Articles Containing Functional Polymeric Phase Change Materials and Methods of Manufacturing the Same

ABSTRACT

An article comprises a substrate and a functional polymeric phase change material bound to the substrate. In some aspects the functional polymeric phase change material is chemically bound to the substrate and can be accomplished by at least one of covalent bonding or electrovalent bonding. The functional polymeric phase change material can comprise a reactive function selected from the group consisting of an acid anhydride group, an alkenyl group, an alkynyl group, an alkyl group, an aldehyde group, an amide group, an amino group and their salts, a N-substituted amino group, an aziridine, an aryl group, a carbonyl group, a carboxy group and their salts, an epoxy group, an ester group, an ether group, a glycidyl group, a halo group, a hydride group, a hydroxy group, an isocyanate group, a thiol group, a disulfide group, a silyl or silane group, an urea group, and an urethane group, and wherein the substrate comprises at least one of cellulose, wool, fur, leather, polyester and nylon. Methods of producing the articles are also disclosed.

RELATED APPLICATIONS

The present application is related to commonly owned and assignedapplication Ser. No. 12/174,607, entitled Functional Polymeric PhaseChange Materials and Methods of Manufacturing the Same, filed on Jul.16, 2008 and application Ser. No. 12/174,609, entitled FunctionalPolymeric Phase Change Materials, filed on Jul. 16, 2008. The details ofthese applications are incorporated herein by reference in theirentirety.

PRIORITY

The present application is a continuation-in-part, and claims priorityunder 35 U.S.C. §120, to the same commonly owned US Patent Applicationsidentified above, namely, U.S. patent application Ser. Nos. 12/174,607and 12/174,609, filed on Jul. 16, 2008. The details of theseapplications are incorporated herein by reference in their entirety.

FIELD OF THE INVENTION

In general, the present invention relates to articles containingfunctionally reactive phase change materials and methods formanufacturing those materials. In particular, but not by way oflimitation, the present invention relates to articles containingfunctionally reactive polymeric phase change materials that form acovalent or an electrovalent interaction with another material.

BACKGROUND OF THE INVENTION

The modification of textiles to provide temperature regulatingproperties through the generalized use of phase change materials (PCMs)is known. The use of microencapsulated PCM (mPCM), their methods ofmanufacture and applications thereof have also been widely disclosed.For example, the following references all use microcapsules in theirapplication:

-   -   1. U.S. Pat. No. 5,366,801—Fabric with Reversible Enhanced        Thermal Properties    -   2. WO0212607—Thermal Control Nonwoven    -   3. U.S. Pat. No. 6,517,648—Process for Preparing a Non-Woven        Fibrous Web    -   4. JP05-156570—Fibrous Structure having Heat Storage Ability and        its Production    -   5. US20040029472—Method and compound fabric with latent heat        effect    -   6. US20040026659—Composition for Fabricating Phase-Change        Material Microcapsules and a Method for Fabricating the        Microcapsules    -   7. US20040044128—Method and Microcapsule Compound Waterborne        Polyurethane    -   8. US2004011989—Fabric Coating Composition with Latent Heat        Effect and Method for Fabricating the Same    -   9. US20020009473—Microcapsule, Method for its Production, Use of        same, and Coating Liquid with Such    -   10. JP11350240—Production of Fiber having Adhered Microcapsule        on Surface    -   11. JP2003-268679—Yarn having Heat Storage Property and Woven        Fabric using the same.

Microcapsules, however, are expensive, can rupture, need additionalresinous binders for adhesion, and can cause poor fabric flexibility andproperties.

Numerous other disclosures outline the development of temperatureregulating textiles by first manufacturing a fiber that contains a PCMor mPCM. For example, the following all disclose compositions, methodsof manufacture, processes, and fabrics created from syntheticallymanufactured fibers. While this might be acceptable in somecircumstances, the applications disclosed below omit all of the naturalcellulosic and proteinaceous fibers and fabrics such as cotton, flax,leather, wool, silk, and fur. They also do not allow for the posttreatment of synthetic fibers or fabrics.

-   -   12. US20030035951–Multi-Component Fibers having Enhanced        Reversible Thermal Properties and Methods of Manufacturing        Thereof.    -   13. U.S. Pat. No. 4756958—Fiber with Reversible Enhance Thermal        Storage Properties and Fabrics made there from.    -   14. JP5331754—Heat Absorbing and Releasing Nonwoven Fabric of        Conjugate Fiber    -   15. JP6041818—Endothermic and Exothermic Conjugate Fiber    -   16. JP5239716—Thermally Insulating Conjugate Fiber    -   17. JP8311716—Endothermic and Exothermic Conjugate Fiber    -   18. JP5005215—Endothermic and Exothermic Conjugate Fiber    -   19. JP2003027337—Conjugate Fiber Having Heat-Storing and        Heat-Retaining Property    -   20. JP07-053917—Heat-Accumulating and Heat-Insulating Fiber    -   21. JP2003-293223—Endothermic Conjugate Fiber    -   22. JP02289916—Thermal Storage Fiber    -   23. JP03326189—Fiber with Heat Storage Ability    -   24. JP04-219349—Heat Storage Composition    -   25. JP06-234840—Heat Storage Material    -   26. JP Appl. #2001-126109—Heat Storage Fiber, Method of        Producing the same, and Heat Storage Cloth Material    -   27. JP03352078—Heat Storage Material    -   28. JP04-048005—Fabric Product with Heat Storing Ability    -   29. WO0125511—Thermal Energy Storage Materials    -   30. JP02317329—Heat Storage Fiber-Method for Producing the same        and Heat Storage Cloth Material    -   31. WO2004007631—Heat-Storage Material, Composition Therefore,        and uses of these    -   32. JP2003-268358—Heat-Storage Material use around Body    -   33. JP2004-011032—Temperature-Controllable Fiber and Fabric    -   34. JP2004-003087—Heat Storable Composite Fiber and Cloth        Material having Heat-Storing Properties    -   35. JP06200417—Conjugate Fiber Containing Heat-Accumulation        Material and its Production    -   36. CN1317602—Automatic Temp-Regulating Fibre and its Products    -   37. U.S. Pat. No. 5,885,475—Phase Change Materials Incorporated        throughout the Structure of Polymer Fibers

In addition, U.S. Pat. Nos. 4,851,291, 4,871,615, 4,908,238, and5,897,952 disclose the addition of polyethylene glycol (PEG), polyhydricalcohol crystals, or hydrated salt PCM to hollow and non-hollow fibers.The fibers can be natural or synthetic, cellulosic, protein based, orsynthetic hydrocarbon based. The non-hollow fibers have PEG materialsdeposited or reacted on the surface to act like PCM. These areproblematic in that they are very hydrophilic causing excessive moistureabsorption problems, and wash durability problems. There is no knowndisclosure of the use of acrylic, methacrylic polymers or otherhydrophobic polymeric PCMs for these applications.

U.S. Pat. No. 6,004,662 mentions the use of acrylate and methacrylatepolymers with C16 to C18 alkyl side chains as PCMs but not asunencapsulated or functionalized or reacted to the surface of fibroustextiles.

U.S. Pat. Nos. 4,259,198 and 4,181,643 disclose the use of crystallinecrosslinked synthetic resin selected from the group of epoxide resins,polyurethane resins, polyester resins and mixtures thereof whichcontain, as crystallite forming blocks, segments of long-chaindicarboxylic acids or diols as PCMs, but not in conjunction with fibersor textiles.

Specific fiber and textile treatments or finishes in which specificcompounds are reacted onto the substrate to provide some thermal change(usually based on moisture) have been disclosed. These systems are notbased on long side chain alkyl, or long chain glycol acrylates ormethacrylates that undergo a thermal phase change to provide improvedlatent heat effects. Examples include:

-   -   38. JP2003-020568—Endothermic Treating Agent for Fiber Material    -   39. JP2002-348780—Hygroscopic and Exothermic Cellulose-Based        Fiber    -   40. JP2001-172866—Hygroscopic and Exothermic Cellulose-Based        Fiber Product having Excellent Heat Retaining Property    -   41. JP 11-247069—Warm Retainable Exothermic Cloth

Various disclosures describe the use of acrylic or methacryliccopolymers containing long chain alkyl moieties for textile finishes butonly for properties such as grease repellency, soil resistance,permanent press properties, and quickness of drying. They do notdisclose or mention the use of high purity polymers as PCMs, latent heatstorage treatments or textile finishes which can impart temperatureregulation and improved comfort. More specifically, they do not discloseadvantageous polymer architecture such as mol. wt., mol. wt.distribution or specific copolymer architecture. Example include:

-   -   42. U.S. Pat. No. 6,679,924—Dye fixatives    -   43. U.S. Pat. No. 6,617,268—Method for protecting cotton from        enzymatic attack by cellulase enzymes    -   44. U.S. Pat. No. 6,617,267—Modified textile and other materials        and methods for their preparation    -   45. U.S. Pat. No. 6,607,994—Nanoparticle-based permanent        treatments for textiles    -   46. U.S. Pat. No. 6,607,564—Modified textiles and other        materials and methods for their preparation    -   47. U.S. Pat. No. 6,599,327—Modified textiles and other        materials and methods for their preparation    -   48. U.S. Pat. No. 6,544,594—Water-repellent and soil-resistant        finish for textiles    -   49. U.S. Pat. No. 6,517,933—Hybrid polymer materials    -   50. U.S. Pat. No. 6,497,733—Dye fixatives    -   51. U.S. Pat. No. 6,497,732—Fiber-reactive polymeric dyes    -   52. U.S. Pat. No. 6,485,530—Modified textile and other materials        and methods for their preparation    -   53. U.S. Pat. No. 6,472,476—Oil-and water-repellent finishes for        textiles    -   54. U.S. Pat. No. 6,387,492—Hollow polymeric fibers    -   55. U.S. Pat. No. 6,3803,36—Copolymers and oil-and        water-repellent compositions containing them    -   56. U.S. Pat. No. 6,379,753—Modified textile and other materials        and methods for their preparation    -   57. US20040058006—High affinity nanoparticles    -   58. US20040055093—Composite fibrous substrates having protein        sheaths    -   59. US20040048541—Composite fibrous substrates having        carbohydrate sheaths    -   60. US20030145397—Dye fixatives    -   61. US20030104134—Water-repellent and soil-resistant finish for        textiles    -   62. US20030101522—Water-repellent and soil-resistant finish for        textiles    -   63. US20030101518—Hydrophilic finish for fibrous substrates    -   64. US20030079302—Fiber-reactive polymeric dyes    -   65. US20030051295—Modified textiles and other materials and        methods for their preparation    -   66. US20030013369—Nanoparticle-based permanent treatments for        textiles    -   67. US20030008078—Oil-and water-repellent finishes for textiles    -   68. US20020190408—Morphology trapping and materials suitable for        use therewith    -   69. US20020189024—Modified textiles and other materials and        methods for their preparation    -   70. US20020160675—Durable finishes for textiles    -   71. US20020155771—Modified textile and other materials and        methods for their preparation    -   72. US20020152560—Modified textiles and other materials and        methods for their preparation    -   73. US20020122890—Water-repellent and soil-resistant finish for        textiles    -   74. US20020120988—Abrasion-and wrinkle-resistant finish for        textiles

Although present compositions and methods are functional, they do nottake advantage of the unique nature and functional aspects thataccompanies the use of polymeric materials for the phase changematerial.

SUMMARY OF THE INVENTION

Exemplary embodiments are summarized below. These and other embodimentsare more fully described in the Detailed Description section. It is tobe understood, however, that there is no intention to limit theinvention to the forms described in this Summary of the Invention or inthe Detailed Description. One skilled in the art can recognize thatthere are numerous modifications, equivalents and alternativeconstructions that fall within the spirit and scope of the invention asexpressed in the claims.

In accordance with one aspect an article comprises a substrate and afunctional polymeric phase change material bound to the substrate.

In accordance with another aspect, a precursor for the production of anarticle comprises a functional polymeric phase change material and atleast one other ingredient.

In accordance with another aspect, a method of producing an articlecomprises providing a functional polymeric phase change material,providing a substrate, and combining the functional polymeric phasechange material with the substrate.

Many additional aspects and embodiments are described herein as would berecognized by one of ordinary skill in the art.

BRIEF DESCRIPTION OF THE DRAWINGS

Various objects and advantages and a more complete understanding of thepresent invention are apparent and more readily appreciated by referenceto the following Detailed Description and to the appended claims whentaken in conjunction with the accompanying Drawings wherein:

FIGS. 1 and 2 show representative examples of functional polymeric phasechange materials (FP-PCMs) based on a (meth)acrylate backbone withcrystallizable side chains based on long chain alky groups or long chainether groups respectively where R=reactive functional groups;

FIGS. 1 a and 2 a show representative examples of FP-PCMs based on avinyl ester backbone with crystallizable side chains based on long chainalky groups or long chain ether groups respectively where R=reactivefunctional groups;

FIGS. 1 b and 2 b show representative examples of FP-PCMs based on avinyl ether backbone with crystallizable side chains based on long chainalky groups or long chain ether groups respectively where R =reactivefunctional groups;

FIG. 1 c shows a representative example of an FP-PCM based on apolyolefin backbone with crystallizable side chains based on long chainalky groups where R=reactive functional groups;

FIG. 3 shows a representative example of an FP-PCM based on acrystallizable backbone polymer such as polyesters, polyethers,polyurethanes, polyamides, polyimides, polyacetals, polysulfides,polysulfones, etc where R=reactive functional groups on one end of thepolymer chain;

FIG. 4 is a chart depicting the generic classifications of man-madefibers which can incorporate FP-PCM or be made into wovens, knits,nonwoven or other substrates which can be treated with FP-PCM;

FIGS. 5A-5F are various embodiments of functional polymeric PCMsinteracting with a substrate; and

FIGS. 6A-6D are further embodiments of functional polymeric PCMsinteracting with a substrate.

DETAILED DESCRIPTION

Definitions—The following definitions apply to various elementsdescribed with respect to various aspects of the invention. Thesedefinitions may likewise be expanded upon herein.

As used herein, the term “monodisperse” refers to being substantiallyuniform with respect to a set of properties. Thus, for example, a set ofmicrocapsules that are monodisperse can refer to such microcapsules thathave a narrow distribution of sizes around a mode of the distribution ofsizes, such as a mean of the distribution of sizes. A further example isa set of polymer molecules with similar molecular weights.

As used herein, the term “latent heat” refers to an amount of heatabsorbed or released by a material as it undergoes a transition betweentwo states. Thus, for example, a latent heat can refer to an amount ofheat that is absorbed or released as a material undergoes a transitionbetween a liquid state and a crystalline solid state, a liquid state anda gaseous state, a crystalline solid state and a gaseous state, twocrystalline solid states or crystalline state and amorphous state.

As used herein, the term “transition temperature” refers to anapproximate temperature at which a material undergoes a transitionbetween two states. Thus, for example, a transition temperature canrefer to a temperature at which a material undergoes a transitionbetween a liquid state and a crystalline solid state, a liquid state anda gaseous state, a crystalline solid state and a gaseous state, twocrystalline solid states or crystalline state and amorphous state . . .A temperature at which an amorphous material undergoes a transitionbetween a glassy state and a rubbery state may also be referred to as a“glass transition temperature” of the material.

As used herein, the term “phase change material” refers to a materialthat has the capability of absorbing or releasing heat to adjust heattransfer at or within a temperature stabilizing range. A temperaturestabilizing range can include a specific transition temperature or arange of transition temperatures. In some instances, a phase changematerial can be capable of inhibiting heat transfer during a period oftime when the phase change material is absorbing or releasing heat,typically as the phase change material undergoes a transition betweentwo states. This action is typically transient and will occur until alatent heat of the phase change material is absorbed or released duringa heating or cooling process. Heat can be stored or removed from a phasechange material, and the phase change material typically can beeffectively recharged by a source emitting or absorbing it. For certainimplementations, a phase change material can be a mixture of two or morematerials. By selecting two or more different materials and forming amixture, a temperature stabilizing range can be adjusted for any desiredapplication. The resulting mixture can exhibit two or more differenttransition temperatures or a single modified transition temperature whenincorporated in the articles described herein.

As used herein, the term “polymer” refers to a material that includes aset of macromolecules. Macromolecules included in a polymer can be thesame or can differ from one another in some fashion. A macromolecule canhave any of a variety of skeletal structures, and can include one ormore types of monomeric units. In particular, a macromolecule can have askeletal structure that is linear or non-linear. Examples of non-linearskeletal structures include branched skeletal structures, such thosethat are star branched, comb branched, or dendritic branched, andnetwork skeletal structures. A macromolecule included in a homopolymertypically includes one type of monomeric unit, while a macromoleculeincluded in a copolymer typically includes two or more types ofmonomeric units. Examples of copolymers include statistical copolymers,random copolymers, alternating copolymers, periodic copolymers, blockcopolymers, radial copolymers, and graft copolymers. In some instances,a reactivity and a functionality of a polymer can be altered by additionof a set of functional groups, such as acid anhydride groups, aminogroups and their salts, N-substituted amino groups, amide groups,carbonyl groups, carboxy groups and their salts, cyclohexyl epoxygroups, epoxy groups, glycidyl groups, hydroxy groups, isocyanategroups, urea groups, aldehyde groups, ester groups, ether groups,alkenyl groups, alkynyl groups, thiol groups, disulfide groups, silyl orsilane groups, groups based on glyoxals, groups based on aziridines,groups based on active methylene compounds or other b-dicarbonylcompounds (e.g., 2,4-pentandione, malonic acid, acetylacetone,ethylacetone acetate, malonamide, acetoacetamide and its methylanalogues, ethyl acetoacetate, and isopropyl acetoacetate), halo groups,hydrides, or other polar or H bonding groups and combinations thereof.Such functional groups can be added at various places along the polymer,such as randomly or regularly dispersed along the polymer, at ends ofthe polymer, on the side, end or any position on the crystallizable sidechains, attached as separate dangling side groups of the polymer, orattached directly to a backbone of the polymer. Also, a polymer can becapable of cross-linking, entanglement, or hydrogen bonding in order toincrease its mechanical strength or its resistance to degradation underambient or processing conditions. As can be appreciated, a polymer canbe provided in a variety of forms having different molecular weights,since a molecular weight of the polymer can be dependent upon processingconditions used for forming the polymer. Accordingly, a polymer can bereferred to as having a specific molecular weight or a range ofmolecular weights. As used herein with reference to a polymer, the term“molecular weight” can refer to a number average molecular weight, aweight average molecular weight, or a melt index of the polymer.

Examples of polymers (including those polymers used for crosslinkers andbinders) include polyhydroxyalkonates, polyamides, polyamines,polyimides, polyacrylics (e.g., polyacrylamide, polyacrylonitrile, andesters of methacrylic acid and acrylic acid), polycarbonates (e.g.,polybisphenol A carbonate and polypropylene carbonate), polydienes(e.g., polybutadiene, polyisoprene, and polynorbornene), polyepoxides,polyesters (e.g., polycaprolactone, polyethylene adipate, polybutyleneadipate, polypropylene succinate, polyesters based on terephthalic acid,and polyesters based on phthalic acid), polyethers (e.g., polyethyleneglycol or polyethylene oxide, polybutylene glycol, polypropylene oxide,polyoxymethylene or paraformaldehyde, polytetramethylene ether orpolytetrahydrofuran, and polyepichlorohydrin), polyfluorocarbons,formaldehyde polymers (e.g., urea-formaldehyde, melamine-formaldehyde,and phenol formaldehyde), natural polymers (e.g., polysaccharides, suchas cellulose, chitan, chitosan, and starch; lignins; proteins; andwaxes), polyolefins (e.g., polyethylene, polypropylene, polybutylene,polybutene, and polyoctene), polyphenylenes, silicon-containing polymers(e.g., polydimethyl siloxane and polycarbomethyl silane), polyurethanes,polyvinyls (e.g., polyvinyl butyral, polyvinyl alcohol, esters andethers of polyvinyl alcohol, polyvinyl acetate, polystyrene,polymethylstyrene, polyvinyl chloride, polyvinyl pryrrolidone,polymethyl vinyl ether, polyethyl vinyl ether, and polyvinyl methylketone), polyacetals, polyarylates, alkyd-based polymers (e.g., polymersbased on glyceride oil), copolymers (e.g., polyethylene-co-vinyl acetateand polyethylene-co-acrylic acid), and mixtures thereof. The termpolymer is meant to be construed to include any substances that becomeavailable after the filing of this application and that exhibit thegeneral polymeric properties described above.

As used herein, the term “chemical bond” and its grammatical variationsrefer to a coupling of two or more atoms based on an attractiveinteraction, such that those atoms can form a stable structure. Examplesof chemical bonds include covalent bonds and ionic bonds. Other examplesof chemical bonds include hydrogen bonds and attractive interactionsbetween carboxy groups and amine groups.

As used herein, the term “molecular group” and obvious variationsthereof, refers to a set of atoms that form a portion of a molecule. Insome instances, a group can include two or more atoms that arechemically bonded to one another to form a portion of a molecule. Agroup can be neutral on the one hand or charged on the other, e.g.,monovalent or polyvalent (e.g., bivalent) to allow chemical bonding to aset of additional groups of a molecule. For example, a monovalent groupcan be envisioned as a molecule with a set of hydride groups removed toallow chemical bonding to another group of a molecule. A group can beneutral, positively charged, or negatively charged. For example, apositively charged group can be envisioned as a neutral group with oneor more protons (i.e., H+) added, and a negatively charged group can beenvisioned as a neutral group with one or more protons removed. A groupthat exhibits a characteristic reactivity or other set of properties canbe referred to as a functional group, reactive function or reactivefunctional groups. Examples of reactive functional groups include suchas acid anhydride groups, amino groups, N-substituted amino groups andtheir salts, amide groups, carbonyl groups, carboxy groups and theirsalts, cyclohexyl epoxy groups, epoxy groups, glycidyl groups, hydroxygroups, isocyanate groups, urea groups, aldehyde groups, ester groups,ether groups, alkenyl groups, alkynyl groups, thiol groups, disulfidegroups, silyl or silane groups, groups based on glyoxals, groups basedon aziridines, groups based on active methylene compounds or otherb-dicarbonyl compounds (e.g., 2,4-pentandione, malonic acid,acetylacetone, ethylacetone acetate, malonamide, acetoacetamide and itsmethyl analogues, ethyl acetoacetate, and isopropyl acetoacetate), halogroups, hydrides, or other polar or H bonding groups and combinationsthereof.

As used herein, the term “covalent bond” means a form of chemicalbonding that is characterized by the sharing of pairs of electronsbetween atoms, or between atoms and other covalent bonds.Attraction-to-repulsion stability that forms between atoms when theyshare electrons is known as covalent bonding. Covalent bonding includesmany kinds of interactions, including a-bonding, 7-bonding, metal-metalbonding, agostic interactions, and three-center two-electron bonds.

The reactive function could be of various chemical natures. For example,reactive functions capable of reacting and forming electrovalent bondsor covalent bonds with reactive functions of various substrates, e.g.cotton, wool, fur, leather, polyester and textiles made from suchmaterials, as well as other base materials. For example, materials madefrom natural, regenerated or synthetic polymers/fibers/materials mayform a electrovalent bond. Further examples of such substrates includevarious types of natural products including animal products such asalpaca, angora, camel hair, cashmere, catgut, chiengora, llama, mohair,silk, sinew, spider silk, wool, and protein based materials, varioustypes of vegetable based products such as bamboo, coir, cotton, flax,hemp, jute, kenaf, manila, pinfa, raffia, ramie, sisal, and cellulosebased materials; various types of mineral based products such asasbestos, basalt, mica, or other natural inorganic fibers. Generally,man-made fibers are classified into three classes, those made fromnatural polymers, those made from synthetic polymers and those made frominorganic materials. FIG. 4 depicts the generic classification of manmade fibers with their International Bureau for the Standardization ofMan-Made Fibres (BISFA) codes. A general description follows.

Fibers from Natural Polymers—The most common natural polymer fibre isviscose, which is made from the polymer cellulose obtained mostly fromfarmed trees. Other cellulose-based fibers are cupro, acetate andtriacetate, lyocell and modal. The production processes for these fibersare given within this disclosure. Less common natural polymer fibers aremade from rubber, alginic acid and regenerated protein.

Fibers from Synthetic Polymers—There are very many synthetic fibers,i.e. organic fibers based on petrochemicals. The most common arepolyester, polyamide (often called nylon), acrylic and modacrylic,polypropylene, the segmented polyurethanes which are elastic fibersknown as elastanes (or spandex in the USA), and specialty fibers such asthe high performance aramids.

Fibers from Inorganic Materials—The inorganic man-made fibers are fibersmade from materials such as glass, metal, carbon or ceramic. Thesefibers are very often used to reinforce plastics to form composites.

Examples of suitable reactive functional groups include functionalgroups such as acid anhydride groups, amino groups, N-substituted aminogroups and their salts, amide groups, carbonyl groups, carboxy groupsand their salts, cyclohexyl epoxy groups, epoxy groups, glycidyl groups,hydroxy groups, isocyanate groups, urea groups, aldehyde groups, estergroups, ether groups, alkenyl groups, alkynyl groups, thiol groups,disulfide groups, silyl or silane groups, groups based on glyoxals,groups based on aziridines, groups based on active methylene compoundsor other b-dicarbonyl compounds (e.g., 2,4-pentandione, malonic acid,acetylacetone, ethylacetone acetate, malonamide, acetoacetamide and itsmethyl analogues, ethyl acetoacetate, and isopropyl acetoacetate), halogroups, hydrides, or other polar or H bonding groups and combinationsthereof.

Further details of the variety of examples of reactive functions andfunctional groups that may be used in accordance with one or moreaspects of the present invention can be found in commonly owned andco-pending patent application Ser. Nos. 12/174,607 and 12/174,609, thedetails of which have been incorporated by reference into thisdisclosure. It should be clearly understood that by providing examplesof specific compositions and methods in the later part of thisdescription, applicant does not intend to limit the scope of the claimsto any of those specific composition. To the contrary, it is anticipatedthat any combination of the functional groups, polymeric phase changematerials, and articles described herein may be utilized to achieve thenovel aspects of the present invention. The claims are not intended tobe limited to any of the specific compounds described in this disclosureor any disclosure incorporated herein.

Several publications referenced herein deal with polymeric PCMs (P-PCM),which in a way, present an intermediate case between the solid-liquidPCMs and the solid-solid PCMs. P-PCMs are solid both prior to phasechange and after it. The difference is in their degree of structure. Atlower temperatures, that degree is greater than that at the elevatedtemperature, so that at a temperature of phase change, P-PCM convertsfrom the more structured form into its less structured one. Typically,in the more structures form, some sections of the polymer are betteraligned and more closely compacted. The better aligned sections resemblecrystallites. Therefore, the phase change on heating P-PCM is alsoreferred to as change from a more crystallized form to a lesscrystallized form. Differently put, at the elevated temperatures (abovethe transition temperature), P-PCMs are essentially amorphous. At thelower temperatures (below the transition temperature) they have a degreeof crystallinity. Similarly, the changes on heat absorption and on heatrelease could be referred to as decrystallization and recrystallization,respectively. The related enthalpy could also be referred to as enthalpyof decrystallization.

Typically, P-PCMs have sections that are capable of being better alignedand more closely compacted. Such sections could be referred to ascrystallizable sections. In some embodiments, the functional polymericPCM described herein in accordance with various aspects of the presentinvention comprises at least one such crystallizable section. Accordingto an embodiment of the invention, the polymer comprises a backbone andside chains. Preferably, the side chains form a crystallizable section.

As used here, the term “reactive function” means a chemical group (or amoiety) capable of reacting with another chemical group to form acovalent or an electrovalent bond, examples of which are given above.Preferably, such reaction is doable at relatively low temperatures, e.g.below 200° C., more preferably below 100° C., and at conditions suitableto handle delicate substrates, e.g. textile. As used herein the term“carrying a function” and obvious variations of this term, means havinga function bound to it, e.g. covalently or electrovalently.

The reactive function could be placed on (carried on or covalently boundor electrovalently bonded to) any part of the FP-PCM molecule, e.g. on aside chain, along the backbone chain or on at least one of the ends ofthe backbone chain or side chain. According to various embodiments ofthe invention, the FP-PCM comprises multiple reactive functions andthose functions are spread at substantially regular intervals,stereospecifically or randomly along the molecule, e.g. along thebackbone chain. Any combination of these is also possible.

The molecular weight of FP-PCM of the present invention is preferably ofat least 500 Daltons, more preferably at least 2000 Daltons. Preferablythe weight of the crystallizable section forms at least 20%, morepreferably at least 50%, and most preferably at least 70% of the totalweight of the FP-PCM.

The FP-PCM of the present invention has a single phase changetemperature or multiple such temperatures. According to one embodiment,the FP-PCM has at least one phase change temperature in the rangebetween −10° C and 100° C., preferably between 10° C. and 60° C. and aphase change enthalpy of at least 25 J/g.

The phase change at each of the temperatures has its own enthalpy, sothat according to some of the embodiments, the article has a singlephase change enthalpy and, according to other embodiments, multiple suchenthalpies. As used herein, the term “overall phase change enthalpy”refers to the enthalpy of phase change in the case of article with asingle phase change temperature and to the combined enthalpies in caseof multiple phase change temperatures. According to an embodiment of theinvention, the article has an overall phase change enthalpy of at least2.0 Joules/gram (J/g) or 10 J/m².

While each of the FP-PCM molecules carries at least one reactivefunction, large FP-PCM molecules may carry multiple reactive functions.According to an embodiment of the invention, an FP-PCM carries at leastone reactive function per 10,000 Daltons of the molecular weight andpreferably two reactive functions.

As indicated, the reactive function of the FP-PCM of the presentinvention should be capable of forming covalent or electrovalent bondswith various articles, compounds and other molecules, commonly referredto here as base materials or substrates. According to anotherembodiment, substrates are selected from a group consisting of cotton,wool, fur, leather, polyester and textiles made from such materials.Examples of reactive functions capable of forming covalent bonds areacid anhydride groups, amino groups, N-substituted amino groups,carbonyl groups, carboxy groups, cyclohexyl epoxy groups, epoxy groups,glycidyl groups, hydroxy groups, isocyanate groups, urea groups,aldehyde groups, ester groups, ether groups, alkenyl groups, alkynylgroups, thiol groups, disulfide groups, silyl or silane groups, groupsbased on glyoxals, groups based on aziridines, groups based on activemethylene compounds or other b-dicarbonyl compounds (e.g.,2,4-pentandione, malonic acid, acetylacetone, ethylacetone acetate,malonamide, acetoacetamide and its methyl analogues, ethyl acetoacetate,and isopropyl acetoacetate), halo groups, hydrides, or and combinationsthereof. FP-PCMs capable of forming covalent bonds are disclosed incommonly assigned U.S. patent application Ser. No. 12/174,607, theteaching of which is incorporated herein by reference in its entirety.Examples of reactive functions capable of forming electrovalent bondsare acid functions, basic functions, positively charged complexes andnegatively charged complexes. FP-PCM capable of forming electrovalentbonds such as disclosed in commonly assigned U.S. patent applicationSer. No. 12/174,609, the teaching of which is incorporated herein byreference in its entirety.

According to another embodiment of the invention, the article formingthe substrate further comprises at least one other ingredient. Suitableingredients may be selected from a group consisting of another FP-PCM,another PCM, microcapsules comprising PCM, microcapsules with otheradditives, binders, crosslinkers, blending polymers, compatibilizers,wetting agents, and additives. The FP-PCM may also be bound to the atleast one other ingredient.

According to another embodiment, the functional polymeric phase changematerial is chemically bound to the substrate. Binding may be one ofcovalent binding, electrovalent binding, direct binding, or binding viaa connecting compound. According to another embodiment, binding is suchas the one resulting from a reaction between a reactive function of theFP-PCM and a reactive function of the substrate, preferably the bindingis a result of such reaction. The substrate can be selected from thegroup consisting of textiles such as natural fibers, fur, syntheticfibers, regenerated fibers, woven fabric, knit fabric, nonwoven fabric,foams, paper, leather, plastic or polymeric layers such as plasticfilms, plastic sheets, laminates or combinations of above.

Textiles described herein can be used for any garment or article thatcomes in contact with a human or animal body. This includes hats,helmets, glasses, goggles, masks, scarves, shirts, baselayers, vests,jackets, underwear, lingerie, bras, gloves, liners, mittens, pants,overalls, bibs, socks, hosiery, shoes, boots, insoles, sandals, bedding,sleeping bags, blankets, mattresses, sheets, pillows, textileinsulation, backpacks, sports pads/padding, etc. The textile article cancontain the FP-PCM or can be coated, laminated or molded. For instance,fibers can be manufactured with the FP-PCM contained in the fiber,coated onto the fiber or treated in which the fiber and FP-PCM interact.This is applicable also to any step in a textile manufacturing process.

Articles described herein can be used in conjunction with one or more ofthe following categories of products and articles:

Shipping, storage or packaging containers/equipment such as paper,glass, metal, plastic, ceramic, organic or inorganic materials in theform of envelopes, sleeves, labels, cardboard, wrapping, wires,tiedowns, insulation, cushioning, pads, foams, tarps, bags, boxes,tubes, containers, sheet, film, pouches, suitcases, cases, packs,bottles, jars, lids, covers, cans, jugs, glasses, tins, pails, buckets,baskets, drawers, drums, barrels, tubs, bins, hoppers, totes, truck/shipcontainers or trailers, carts, shelves, racks, etc. These articles canespecially be used in the food shipment, food delivery, medicalshipment, medical delivery, body shipment, etc. industries.

Medical, health, therapeutic, curative, and wound management articlessuch as bandages, wraps, wipes, stents, capsules, drug, deliverydevices, tubes, bags, pouches, sleeves, foams, pads, sutures, wires,etc.

Building, construction, and interior articles where energy managementand off-peak energy demand reduction is desired. These articles caninclude such as upholstery, furniture, beds, furnishings, windows,window coatings, window treatments and coverings, wallboard, insulation,foams, piping, tubes, wiring, laminates, bricks, stones, siding, panelsfor wall or ceiling, flooring, cabinets, building envelopes, buildingwrap, wallpaper, paint, shingles, roofing, frames, etc. The use ofalternative construction techniques and such articles are also includedas straw bale construction, mud or adobe construction, brick or stoneconstruction, metal container construction, etc.

Electronics and electrical articles such as conductors, heat sinks,semiconductors, transistors, integrated circuits, wiring, switches,capacitors, resistors, diodes, boards, coverings, motors, engines, etc.

Articles for use in industries such as automotive, heavy equipment,trucking, food/beverage delivery, cosmetics, civil service, agriculture,hunting/fishing, manufacturing, etc. which incorporate articlesdescribed above.

Cosmetics such as creams, lotions, shampoos, conditioners, bodywash,soaps, hair gels, mousse, lipstick, deodorant, moisturizers, nailpolish, glosses, lipsticks, makeup, eyeliners/eyeshadow, foundations,blushes, mascara, etc.

Controlled release articles in which the FP-PCM creates a barrier whenin one phase and allows movement when in another phase. The barrier canbe due to trapping of the material within the FP-PCM crystalline domainmatrix or physical layers between the materials, etc. This phase shiftto change the barrier characteristics can be triggered by energy such aslight, UV, IR, heat, thermal, plasma, sound, microwave, radiowave,pressure, x-ray, gamma, or any form of radiation or energy. The barriercan prevent movement of or release of such as materials, colors orenergy. A further example is a barrier to liquid materials or theblocking/unblocking of light or color, the change of stiffness orflexibility at various temperatures, etc. Further examples are thecontainment/release of catalysts, chemical reaction control agents(increase or decrease reaction), adhesion, enzymes, dyes, colors,stabilizers for or against light and/or temperature, nano ormicroparticles, temperature or fraud markers, etc.

In addition, the FP-PCM can be incorporated into articles as outlined inthe following commonly assigned patents: For coating, such as in U.S.Pat. No. 5,366,801, Fabric with Reversible Enhanced Thermal Properties;U.S. Pat. No. 6,207,738, Fabric Coating Composition Containing EnergyAbsorbing Phase Change Material; U.S. Pat. No. 6,503,976, Fabric CoatingComposition Containing Energy Absorbing Phase Change Material and Methodof Manufacturing Same; U.S. Pat. No. 6,660,667, Fabric CoatingContaining Energy Absorbing Phase Change Material and Method ofManufacturing Same; U.S. Pat. No. 7,135,424, Coated Articles HavingEnhanced Reversible Thermal Properties and Exhibiting ImprovedFlexibility, Softness, Air Permeability, or Water Vapor TransportProperties; U.S. application Ser. No. 11/342,279, Coated Articles Formedof Microcapsules with Reactive Functional Groups.

For Fibers such as in U.S. Pat. No. 4,756,958, Fiber with ReversibleEnhanced Thermal Storage Properties and Fabrics Made Therefrom; U.S.Pat. No. 6,855,422, Multi-Component Fibers Having Reversible ThermalProperties; U.S. Pat. No. 7,241,497, Multi-Component Fibers HavingReversible Thermal Properties; U.S. Pat. No. 7,160,612, Multi-ComponentFibers Having Reversible Thermal Properties; U.S. Pat. No. 7,244,497,Cellulosic Fibers Having Enhanced Reversible Thermal Properties andMethods of Forming Thereof.

For Fibers, laminates, extruded sheet/film or molded goods, such as inU.S. Pat. No. 6,793,85, Melt Spinable Concentrate Pellets HavingEnhanced Reversible Thermal Properties; U.S. application Ser. No.11/078,656, Polymeric composites having enhanced reversible thermalproperties and methods of forming thereof, PCT App. No. PCT/US07/71373,Stable Suspensions Containing Microcapsules and Methods for PreparationThereof.

These embodiments and articles can be used in any application wheretemperature regulation, temperature buffering, temperature control orlatent heat of fusion is utilized, or any phase transition phenomenon isemployed. These applications may or may not be used in conjunction withhydrophilic properties, hydrophobic properties, moisture absorbing,moisture releasing, organic materials absorption or release, inorganicmaterials absorption or release, crosslinking, anti-microbial,anti-fungal, anti-bacterial, biodegradability, decomposition, anti-odor,odor controlling, odor releasing, grease and stain resistance,stabilization for oxidation or ageing, fire retardant, anti-wrinkle,enhanced rigidity or flexibility, UV or IR screening, impact resistanceor control, color addition, color change, color control, catalytic orreaction control, sound, light, optical, static or energy management,surface tension, surface smoothness, or surface properties control,anti-fraud or brand marking control, controlled release/containment, orcontrolled barrier properties, etc.

In accordance with another aspect a method is provided for theproduction of an article described herein, comprising providing aFP-PCM, providing a substrate and combining the FP-PCM with thesubstrate. According to one embodiment, the substrate carries at leastone reactive function and the combining comprises chemically reacting afunctional group of the FP-PCM with a functional group of the substrate.

According to another aspect, a precursor for the production of thearticle is provided, which precursor comprises a functional polymericphase change material and at least one other ingredient.

According to another aspect, a method for the production of the articlecomprises providing a precursor, providing a substrate, and combiningthe FP-PCM of the precursor with the substrate. The substrate may carryat least one reactive function. Combining the FP-PCM of the precursorwith the substrate comprises chemically reacting a functional group ofthe FP-PCM with a functional group of the substrate.

The selection of a material forming the substrate may be dependent uponvarious considerations, such as its affinity to the FP-PCM, its abilityto reduce or eliminate heat transfer, its breathability, itsdrapability, its flexibility, its softness, its water absorbency, itsfilm-forming ability, its resistance to degradation under ambient orprocessing conditions, and its mechanical strength. In particular, forcertain implementations, a material forming the substrate can beselected so as to include a set of functional groups, such as acidanhydride groups, aldehyde groups, amino groups, N-substituted aminogroups, carbonyl groups, carboxy groups, epoxy groups, ester groups,ether groups, glycidyl groups, hydroxy groups, isocyanate groups, thiolgroups, disulfide groups, silyl groups, groups based on glyoxals, groupsbased on aziridines, groups based on active methylene compounds or otherb-dicarbonyl compounds (e.g., 2,4-pentandione, malonic acid,acetylacetone, ethylacetone acetate, malonamide, acetoacetamide and itsmethyl analogues, ethyl acetoacetate, and isopropyl acetoacetate), orcombinations thereof. At least some of these functional groups can beexposed on a top surface of the substrate and can allow chemical bondingto a set of complementary functional groups included in the embodimentsand additives, thereby enhancing durability of the article duringprocessing or during use. Thus, for example, the substrate can be formedof cellulose and can include a set of hydroxy groups, which canchemically bond to a set of carboxy groups included in the FP-PCM. Asanother example, the substrate can be a proteinacous material and can beformed of silk or wool and can include a set of amino groups, which canchemically bond to those carboxy groups included in the FP-PCM. As canbe appreciated, chemical bonding between a pair of functional groups canresult in the formation of another functional group, such as an amidegroup, an ester group, an ether group, an urea group, or an urethanegroup. Thus, for example, chemical bonding between a hydroxy group and acarboxy group can result in the formation of an ester group, whilechemical bonding between an amino group and a carboxy group can resultin the formation of an amide group.

For certain implementations, a material forming the substrate caninitially lack a set of functional groups, but can be subsequentlymodified so as to include those functional groups. In particular, thesubstrate can be formed by combining different materials, one of whichlacks a set of functional groups, and another one of which includesthose functional groups. These different materials can be uniformlymixed or can be incorporated in separate regions or separate sub-layers.For example, the substrate can be formed by combining polyester fiberswith a certain amount (e.g., 25 percent by weight or more) of cotton orwool fibers that include a set of functional groups. The polyesterfibers can be incorporated in an outer sub-layer, while the cotton orwool fibers can be incorporated in an inner sub-layer, adjacent to otherlayers. As another example, a material forming the substrate can bechemically modified so as to include a set of functional groups.Chemical modification can be performed using any suitable technique,such as using oxidizers, corona treatment, or plasma treatment. Chemicalmodification can also be performed as described in the patent ofKanazawa, U.S. Pat. No. 6,830,782, entitled “Hydrophilic PolymerTreatment of an Activated Polymeric Material and Use Thereof,” thedisclosure of which is incorporated herein by reference in its entirety.In some instances, a material forming the substrate can be treated so asto form radicals that can react with monomers including a set offunctional groups. Examples of such monomers include those withanhydride groups (e.g., maleic anhydride), those with carboxy groups(e.g., acrylic acid), those with hydroxy groups (e.g., hydroxylethylacrylate), and those with epoxy or glycidyl groups (e.g., glycidylmethacrylate). In other instances, a material forming the substrate canbe treated with a set of functional materials to add a set of functionalgroups as well as to provide desirable moisture management properties.These functional materials can include hydrophilic polymers, such aspolyvinyl alcohol, polyglycols, polyacrylic acid, polymethacrylic acid,hydrophilic polyesters, and copolymers thereof. For example, thesefunctional materials can be added during a fiber manufacturing process,during a fabric dyeing process, or during a fabric finishing process.Alternatively, or in conjunction, these functional materials can beincorporated into a fabric via exhaust dyeing, pad dyeing, or jetdyeing.

The FP-PCM can be implemented as a coating, laminate, infusion,treatment or ingredient in a coating, laminate, infusion, treatment thatis formed adjacent to, on or within the substrate using any suitablecoating, laminating, infusion, etc. technique. During use, the FP-PCMcan be positioned so that it is adjacent to an internal compartment oran individual's skin, thus serving as an inner coating. It is alsocontemplated that the FP-PCM can be positioned so that it is exposed toan outside environment, thus serving as an outer coating. The FP-PCMcovers at least a portion of the substrate. Depending on characteristicsof the substrate or a specific coating technique that is used, theFP-PCM can penetrate below the top surface and permeate at least aportion of the substrate. While two layers are described, it iscontemplated that the article can include more or less layers for otherimplementations. In particular, it is contemplated that a third layercan be included so as to cover at least a portion of a bottom surface ofthe substrate. Such a third layer can be implemented in a similarfashion as the FP-PCM or can be implemented in another fashion toprovide different functionality, such as water repellency, stainresistance, stiffness, impact resistance, etc.

In one embodiment, the FP-PCM is blended with a binder which may alsocontain a set of microcapsules that are dispersed in the binder. Thebinder can be any suitable material that serves as a matrix within whichthe FP-PCM and possibly also the microcapsules are dispersed, thusoffering a degree of protection to the FP-PCM and microcapsules againstambient or processing conditions or against abrasion or wear during use.For example, the binder can be a polymer or any other suitable mediumused in certain coating, laminating, or adhesion techniques. For certainimplementations, the binder is desirably a polymer having a glasstransition temperature ranging from about −110° C. to about 100° C.,more preferably from about −110° C. to about 40° C. While a polymer thatis water soluble or water dispersible can be particularly desirable, apolymer that is water insoluble or slightly water soluble can also beused as the binder for certain implementations.

The selection of the binder can be dependent upon variousconsiderations, such as its affinity for the FP-PCM and/or microcapsulesor the substrate, its ability to reduce or eliminate heat transfer, itsbreathability, its drapability, its flexibility, its softness, its waterabsorbency, its coating-forming ability, its resistance to degradationunder ambient or processing conditions, and its mechanical strength. Inparticular, for certain implementations, the binder can be selected soas to include a set of functional groups, such as acid anhydride groups,amino groups and their salts, N-substituted amino groups, amide groups,carbonyl groups, carboxyl groups and their salts, cyclohexyl epoxygroups, epoxy groups, glycidyl groups, hydroxyl groups, isocyanategroups, urea groups, aldehyde groups, ester groups, ether groups,alkenyl groups, alkynyl groups, thiol groups, disulfide groups, silyl orsilane groups, groups based on glyoxals, groups based on aziridines,groups based on active methylene compounds or other b-dicarbonylcompounds (e.g., 2,4-pentandione, malonic acid, acetylacetone,ethylacetone acetate, malonamide, acetoacetamide and its methylanalogues, ethyl acetoacetate, and isopropyl acetoacetate), halo groups,hydrides, or other polar or H bonding groups and combinations thereof.

These functional groups can allow chemical bonding to a complementaryset of functional groups included in either of, or any of, the FP-PCM,the microcapsules and the substrate, thereby enhancing durability of thearticle during processing or during use. Thus, for example, the bindercan be a polymer that includes a set of epoxy groups, which canchemically bond to a set of carboxy groups included in the FP-PCM and/orthe microcapsules. As another example, the binder can be a polymer thatincludes a set of isocyanate groups or a set of amino groups, which canchemically bond with those carboxy groups included in the FP-PCM,microcapsules, or substrate.

In some instances, a set of catalysts can be added when forming thecoating composition. Such catalysts can facilitate chemical bondingbetween complementary functional groups, such as between those includedin the binder and those included in the microcapsules. Examples ofmaterials that can be used as catalysts include boron salts,hypophosphite salts (e.g., ammonium hypophosphite and sodiumhypophosphite), phosphate salts, tin salts (e.g., salts of Sn.sup.+2 orSn.sup.+4, such as dibutyl tin dilaurate and dibutyl tin diacetate), andzinc salts (e.g., salts of Zn.sup.+2). A desirable amount of a tin saltor a zinc salt that is added to the coating composition can range fromabout 0.001 to about 1.0 percent by dry weight, such as from about 0.01to about 0.1 percent by dry weight. A desirable amount of a boron saltor a phosphate salt that is added to the coating composition can rangefrom about 0.1 to about 5 percent by dry weight, such as from about 1 toabout 3 percent by dry weight. Other examples of materials that can beused as catalysts include alkylated metals, metal salts, metal halides,and metal oxides, where suitable metals include Sn, Zn, Ti, Zr, Mn, Mg,B, Al, Cu, Ni, Sb, Bi, Pt, Ca, and Ba. Organic acids and bases, such asthose based on sulfur (e.g., sulfuric), nitrogen (e.g., nitric),phosphorous (e.g., phosphoric), or halides (e.g., F, Cl, Br, and I), canalso be used as catalyst. Further examples of materials that can be usedas catalysts include acids such as citric acid, itaconic acid, lacticacid, fumaric acid, and formic acid.

Bonds between substrate, functional phase change material, binder and/ormicrocapsules are, according to various embodiments, covalent,electrovalent or various combinations of those. Binding could be director indirect, e.g. via a connecting compound. According to someembodiments, the connecting compound is selected from a group consistingof functional polymeric phase change material and microcapsules.According to another embodiment, the functional polymeric phase changematerial forms a binder for at least a portion of a second PCM.

According to another embodiment, the reactive function of the FP-PCM canbe converted into another reactive function, which is more suitable forreacting with particular substrates.

According to another embodiment, the reactive function of the FP-PCMcould be of various chemical nature. For example, reactive functionscapable of reacting and forming covalent or electrovalent bonds withreactive functions of various substrates, e.g. cotton, wool, furleather, polyester and textiles made from such materials.

According to another embodiment of the invention, the reactive functioncan be any of the following: 1) glycidyl or epoxy such as from glycidylmethacrylate or glycidyl vinyl ether; 2) anhydride such as from maleicanhydride or itaconic anhydride; 3) isocyanate such as from isocyanatomethacrylate, TMI® from Cytec Ind. or blocked isocyanates such as2-(0-[1′-methylproplyideneamino]carboxyamino)ethyl methacrylate; 4)amino or amine-formaldehyde such as from N-methylolacrylamide; and 5)silane such as from methacryloxypropyltriethoxysilane. Such reactivefunctions can react with OH functional groups of cellulosic basedtextiles such as cotton; with amine functional groups of proteinaceousbased textiles such as wool, fur or leather; with hydroxyl or carboxylgroups of polyester based textiles and with amide functional groups ofnylon functional resins.

According to still another embodiment of the invention, the reactivefunction is a double bond, capable of binding to another double bond,providing a cross-linking point, etc.

The reactive function of the FP-PCM can assume a positive charge andbind electrovalently with a negative charge on the substrate. Accordingto another embodiment, the reactive function can assume a negativecharge and bind electrovalently with a positive charge on the substrate.According to another embodiment, the reactive functions of both thesubstrate and the FP-PCM and/or microcapsule are negatively charged andbinding is via a multivalent cation, which acts as a cross-linker.According to still another embodiment, the reactive functions of boththe substrate and the FP-PCM and/or microcapsule are positively chargedand binding is via a multivalent anion, which acts as a cross-linker.The cross-linking multivalent cation, anion or both could be organic orinorganic.

An article constructed in accordance with various aspects of the presentinvention can have a single phase change temperature or multiple phasechange temperatures, e.g. in cases wherein the FP-PCM has multiple typesof crystallizable sections or cases wherein the article comprisesmultiple FP-PCMs of different types. An article constructed inaccordance with aspects of the present invention has at least one phasechange temperature in the range between −10° C. and 100° C., preferablybetween 10° C. and 60° C. and phase change enthalpy of at least 2.0Joules/gram (J/g) or 10 J/m². According to other embodiments, thefunctional polymeric phase change material comprises hydrophiliccrystallizable section, hydrophobic crystallizable section or both. Asexample, an AB block copolymer, made of segments such as polystearylmethacrylate and polyethylene glycol methacrylate would have twodifferent phase change temperatures and hydrophilic/hydrophobicproperties. One phase change temperature from the stearyl hydrophobiccrystallizable side chains and another phase change temperature from theglycol hydrophilic crystallizable side chains.

The phase change at each of the temperatures has its own enthalpy, sothat the article has according to some of the embodiments a single phasechange enthalpy and, according to others, multiple such enthalpies.According to an embodiment of the invention, the article has an overallphase change enthalpy of at least 2.0 Joules/gram (J/g) or 10 J/m².

According to another aspect, the present invention provides a precursorfor the production of an article according to the second aspect, whichprecursor comprises the functional polymeric phase change material andat least one other ingredient. The one other ingredient is selected froma group consisting of an organic solvent, an aqueous solvent, anotherFP-PCM, another PCM, microcapsules comprising PCM, microcapsules withother additives, binders, crosslinkers, blending polymers,compatibilizers, wetting agents, catalysts and additives, and theircombinations. Examples of precursors are formulations used for thecoating, dyeing, dipping, spraying, brushing, padding, printing, etc. ofsubstrates, the predispersion of FP-PCMs for addition to manufacturinglines such as injecting into fiber dope on spin lines, Colorant and tintformulations, additive masterbatches or dispersions, neutralizing or pHadjusting solutions, the formulation of plastic pellets or masterbatchesfor extrusion and formation of melt spun fibers, molded parts, film,sheets or laminated products. These are described in cited and includedOutlast patents and applications above.

According to another embodiment, a method is provided for the productionof an article, comprising providing a precursor, providing a substrateand combining the FP-PCM of the precursor with the substrate. Thesubstrate preferably carries at least one reactive function andcombining the FP-PCM of the precursor with the substrate compriseschemically reacting a functional group of the FP-PCM with a functionalgroup of the substrate.

Further examples of binders or crosslinkers are polymers, oligomers ormolecules with multiple reactive functional groups which can interact orbond with another of the same, another FP-PCM, another PCM,microcapsules comprising PCM, microcapsules with other additives,binders, crosslinkers, blending polymers, compatibilizers, wettingagents, additives, etc. The bonds or interactions can be either covalentor ionic.

For certain implementations, a set of reactive components or modifierscan also be added when forming the composition. Such modifiers can allowcross-linking of the FP-PCM and/or binder to provide improvedproperties, such as durability and other properties. Examples ofmaterials that can be used as modifiers include polymers, such asmelamine-formaldehyde resins, urea-formaldehye resins, polyanhydrides,urethanes, epoxies, acids, polyurea, polyamines or any compound withmultiple reactive functional groups. A desirable amount of a modifierthat is added to the coating composition can range from about 1 to about20 percent by dry weight, such as from about 1 to about 5 percent by dryweight. Also, a set of additives can be added when forming thecomposition. In some instances, these additives can be contained withinthe microcapsules. For examples of additives include those that improvewater absorbency, water wicking ability, water repellency, stainresistance, dirt resistance, and odor resistance. Additional examples ofadditives include anti-microbials, flame retardants, surfactants,dispersants, and thickeners. Further examples of additives and modifiersare set forth below.

Moisture management, hydrophilic and polar materials—such as includingor based on acids, glycols, salts, hydroxy group-containing materials(e.g., natural hydroxy group-containing materials), ethers, esters,amines, amides, imines, urethanes, sulfones, sulfides, naturalsaccharides, cellulose, sugars and proteins

Grease, dirt and stain resistance—such as non-functional, non-polar, andhydrophobic materials, such as fluorinated compounds, silicon-containingcompounds, hydrocarbons, polyolefins, and fatty acids.

Anti-microbial, Anti-fungal and Anti-bacterial—such as complexingmetallic compounds based on metals (e.g., silver, zinc, and copper),which cause inhibition of active enzyme centers. copper andcopper-containing materials (e.g., salts of Cu.+2 and Cu.+), such asthose supplied by Cupron Ind., silver and silver-containing materialsand monomers (e.g., salts of Ag, Ag.+, and Ag+2), such as supplied asULTRA-FRESH by Thomson Research Assoc. Inc. and as SANITIZED Silver andZinc by Clariant Corp. oxidizing agents, such as including or based onaldehydes, halogens, and peroxy compounds that attack cell membranes(e.g., supplied as HALOSHIELD by Vanson HaloSource Inc.)2,4,4′-trichloro-2′-hydroxy dipenyl ether (e.g., supplied as TRICLOSAN),which inhibits growth of microorganisms by using an electro-chemicalmode of action to penetrate and disrupt their cell walls. quaternaryammonium compounds, biguanides, amines, and glucoprotamine (e.g.,quaternary ammonium silanes supplied by Aegis Environments or asSANITIZED QUAT T99-19 by Clariant Corp. and biguanides supplied asPURISTA by Avecia Inc.) chitosan castor oil derivatives based onundecylene acid or undecynol (e.g., undecylenoxy polyethylene glycolacrylate or methacrylate).

For certain implementations, the layers can have a loading level of theFP-PCM alone or in combination with microcapsules ranging from about 1to about 100 percent by dry weight, most preferably from about 10% toabout 75%. These FP-PCM, binders, additives and microcapsules can differfrom each other or be the same such as by being liquids or solids atroom temperature, having different shapes or sizes, by including shellsformed of a different material or including different functional groups,or by containing a different phase change material or a combinationthereof.

According to another embodiment, an article comprises a substrate and astarch or modified starch. Starch is a polymer, mainly of glucose, hascrystallizable sections and carries hydroxyl groups. As such it issuitable as an FP-PCM for use in articles constructed in accordance withaspects of the present invention. In most cases, starch consists of bothlinear and branched chains. Different starches comprise various degreesof crystallizable sections, as found e.g. in standard differentialscanning calorimetry (DSC) analysis. The crystallizable section consistsof aligning side chains on the branched starch. Temperature andelevation, optionally combined with increased moisture leads todecrystallization (which is sometimes referred to as gelatinization). Atlower temperature (and moisture), recrystallization takes place. Starchis hydrophilic, and, as such, also provides both for extension of thetemperature regulating capacity of the FP-PCM and for recharging of theFP-PCM. Another feature of using starch and its derivatives, as well assome other hydrophilic FP-PCMs is the ability to adjust its transitiontemperature by adjusting its moisture content. Typically, the higher themoisture, the lower is the transition temperature.

According to various embodiments of the invention, various naturalstarches may be used, including, but not limited to, corn starch, potatostarch and wheat starch. According to other embodiments, modified starchmay be used, e.g. starch modified specifically for the article of thepresent invention or commercially available, modified starch. Accordingto further embodiments, such modified starch is a result of acidhydrolysis for lowering its molecular weight (e.g. acid thinning) and/ora result of separating a fraction of it for enrichment in one of amylaseor amylopectin. According to other embodiments, the starch to be used asan FP-PCM is chemically modified by attaching to it a new reactivefunction. According to various other embodiments, thechemically-modified starch is selected from commercially-available,chemically modified starches prepared for applications such as the foodindustry, the paper industry and others, e.g. hydroxyethyl starch,hydroxypropyl starch, starch acetate, starch phosphate, starch, cationicstarches, anionic starches and their combinations. Modified starches andmethods of their production are described in Chapter 16 of CornChemistry and Technology, edited by Watson and Ramstad, published byAmerican Association of Cereal Chemists Inc., the teaching of which isincorporated herein by reference.

In accordance with one aspect the starch or modified starch is bound tothe substrate via a covalent bond. According to another aspect it isbound via an electrovalent bond. According to various other embodiments,the covalently bound starch is selected from a group consisting ofnatural starch, thinned starch, amylase-enriched starch,amylopectin-enriched starch, hydroxyethyl starch, hydroxypropyl starch,starch acetate, starch phosphate, starch, cationic starches, anionicstarches and their combinations. According to other embodiments, theelectro-valently bound starch is selected from a group consisting ofstarch acetate, starch phosphate, starch, cationic starches, anionicstarches and their combinations.

An article constructed in accordance with one aspect of the presentinvention comprises a substrate and at least one of gelatin, gelatinsolutions and modified gelatin. Gelatin is a polymer mainly containingrepeating sequences of glycine-X-Y-triplets, where X and Y arefrequently proline and hydroxyproline amino acids. These sequences areresponsible for the triple helical structure of gelatins and theirability to form thermally and reversible gels.

The formation of these phase changing structures are greatly dependenton the molecular weight, molecular structure, degree of branching,gelatin extraction process from collagen, natural source of collagen,temperature, pH, ionic concentration, crosslinks, reactive groups,reactive group modifications, presence of iminoacids, purity, solutionconcentrations, etc.

Gelatins can provide for latent heat properties as outlined in “Studiesof the Cross-Linking Process in Gelatin Gels. III. Dependence of MeltingPoint on Concentration and Molecular Weight”: Eldridge, J. E., Ferry, J.D.; Journal of Physical Chemistry, 58, 1954, pp 992-995.

Gelatin can be easily modified by reaction and crosslinking with manycompounds such as crosslinkers and modifiers outlined in above detaileddescription. Crosslinking agents such as aldehydes where formaldehydeand glutaraldhyde may be used. Isocyanates and anhydrides may be used toboth modified the properties of the gelatin and provide for reactivefunctional groups for bonding to substrates.

Gelatin is hydrophilic, and as such also provides both for extension ofthe temperature regulating capacity of the FP-PCM and for recharging ofthe FP-PCM. Another important feature of using gelatins and itsderivatives, as well as some other hydrophilic FP-PCM is the ability toadjust its transition temperature by adjusting its moisture content andpolymer structure, i.e. molecular weight.

According to one embodiment, in an article, the gelatin or modifiedgelatin is bound to the substrate in a covalent bond or an electrovalentbond. According to various embodiments the gelatin can be in the form ofa solution which is contained within the substrate.

FIGS. 1 and 2 are schematic drawings of FP-PCMs used in accordance withan article constructed in accordance with various aspects of the presentinvention. Both are composed of a backbone chain and side chains. TheFP-PCM in FIG. 1 represent long chain alkyl polyacrylate orpolymethacrylate, and 1 a-1 c where 1 a is long chain alkyl vinylesters, 1 b is long chain vinyl ethers and 1 c is long chain alkylolefins.

FIGS. 2 a and 2 b represent long chain glycol polyacrylates orpolymethacrylates, where 2 a is long chain glycol vinyl esters and 2 bis long chain glycol vinyl ethers.

In FIGS. 1 and 2, R represents one or more of the reactive functions(s)described above. In those figures, the functions are drawn along thebackbone, but that is only one option. As indicated above, the functionscould also be placed at the end(s) of the backbone, on the side chainsand any combination of those. Each FP-PCM may have a single or multiplereactive functions. FP-PCM may also carry multiple reactive functions ofa similar chemical nature or a combination of reactive functions ofdifferent chemical nature.

With reference to FIGS. 5A-5F, FIG. 5A drawing depicts an acidic or lowpH carboxyl functional FP-PCM ionically interacting with a basic or highpH amino functional substrate. FIG. 5B depicts basic or high pH aminofunctional FP-PCM ionically interacting with an acidic or low pHcarboxyl functional substrate. FIG. 5C depicts basic or high pH aminofunctional FP-PCM and a basic or high pH amino functional substratebeing neutralized and ionically bound or “crosslinked” with an anionsuch as an amine. FIG. 5D depicts an acidic or low pH carboxylfunctional FP-PCM and an acidic or low pH carboxyl functional substratebeing neutralized and ionically bound or “crosslinked” with a cationsuch as a metal salt. FIG. 5E depicts basic or high pH amino functionalFP-PCM and a basic or high pH amino functional substrate beingneutralized and ionically bound or “crosslinked” with negatively chargedorganic compound such as dicarboxy functional polymer or dicarboxyfunctional FP-PCM. FIG. 5F depicts an acidic or low pH carboxylfunctional FP-PCM and an acidic or low pH carboxyl functional substratebeing neutralized and ionically bound or “crosslinked” with positivelycharged organic compound such as diamine functional polymer or diaminefunctional FP-PCM.

With reference to FIGS. 6A-6D, FIG. 6A depicts a covalent ether bondfrom the reaction of an FP-PCM epoxy and hydroxyl on a cellulosesubstrate. FIG. 6B depicts a covalent urea bond from the reaction of anFP-PCM isocyanate and amine from a proteinceous substrate such as woolor silk. FIG. 6C depicts a covalent urethane bond from the reaction ofan FP-PCM isocyanate on the end of a side chain and hydroxyl from acellulose substrate. FIG. 6D depicts a covalent urea and urethane bondsfrom the reaction of amine function, FP-PCMs, multifunctional isocyanatecrosslinker/binder, and hydroxyl from a cellulose substrate.

EXAMPLES

The following examples are provided as representative of the variouscombinations and embodiments that may be created through the specificfeatures described above and are not meant to be exclusive as the toscope of the claims. Furthermore, it is intended that the examplesprovided below not limit the completeness of the subject matter that ismore appropriately captured by the full disclosure and description. Itis intended that the present description serve as subject matterdisclosure for any combination of the element previously disclosed.

Example 1 Preparation of Polyglycidyl Methacrylate

In a flask equipped with stirrer, condenser, nitrogen purge andtemperature controller was reacted:

Ingredients wt. 1.) n-pentyl propionate (Dow Chemical, Midland MI) 37.62.) Glycidyl methacrylate (Dow Chemical, Midland MI) 85.5 3.) Di-t-amylperoxide (Sigma-Aldrich Corp. Milwaukee WI) 5.4 4.) Di-t-amyl peroxide(Sigma-Aldrich Corp. Milwaukee WI) 0.2

#1 was added to the flask and heated to 152° C. under nitrogen. #2 and#3 were combined and added slowly to reaction flask over 5.5 hours. Thiswas let react and additional 0.5 hours, then #4 added, let react for 1.0hour then cooled to yield a 69.4% solution of polyglycidyl methacrylate.This solution was dried for 4 hrs@120° C. in a forced air oven to yield100% dried polyglycidyl methacrylate.

Example 2 Preparation of Polymeric PCM

In a flask equipped with stirrer, condenser, nitrogen purge andtemperature controller was reacted:

functional Ingredients wt. eqiv. 1.) 95% Palmitic Acid 36.15 0.141 2.)Dried polyGMA from Ex. 1 above 20.06 0.141

#1 was added to the flask and heated to 130° C. under nitrogen. #2 wasadded slowly to reaction flask over 0.5 hours. This was let react andadditional 3.0 hours, then cooled to yield a polymeric PCM with meltpoint of 38.5° C. and 63.1 J/g latent heat.

Example 3 Preparation of Polymeric PCM

In a flask equipped with stirrer, condenser, nitrogen purge andtemperature controller was reacted:

functional Ingredients wt. eqiv. 1.) 95% Myristic Acid 34.67 0.152 2.)Dried polyGMA from Ex. 1 above 21.60 0.152

#1 was added to the flask and heated to 130° C. under nitrogen. #2 wasadded slowly to reaction flask over 0.5 hours. This was let react andadditional 3.0 hours, then cooled to yield a polymeric PCM with meltpoint of 16.1° C. and 29.8 J/g latent heat.

Example 4 Preparation of Polystearyl Methacrylate Polymeric PCM

In a flask equipped with stirrer, condenser, nitrogen purge andtemperature controller was reacted:

Ingredients wt. 1.) n-pentyl propionate (Dow Chemical, Midland MI) 36.12.) SR324 Stearyl methacrylate (Sartomer Co., Exton PA) 94.0 3.)Glycidyl methacrylate (Dow Chemical, Midland MI) 6.0 4.) Di-t-amylperoxide (Sigma-Aldrich Corp. Milwaukee WI) 2.7 5.) Di-t-amyl peroxide(Sigma-Aldrich Corp. Milwaukee WI) 0.5

#1 was added to the flask and heated to 152° C under nitrogen. #2, #3and #4 combined and added slowly to reaction flask over 3.5 hours. Thiswas let react and additional 1.0 hours, #5 added, let react for 1.5 hourthen cooled to yield a 69.7% solution of polystearylmethacrylate-co-glycidyl methacrylate with a melt point of 31.1° C. and83.8 J/g latent heat.

Example 5 Preparation of Wash Durable Temperature Regulating Textileswith Improved Latent Heat Content

Desized, unbleached, undyed cotton fabric was treated by immersing intosolutions of the polymeric PCMs with and without additional crosslinkersor fixatives. The immersed fabrics were then padded to remove excesssolution dried for 4 minutes@190° C. The fabrics where rinsed with warmtap water to remove any unreacted polymer then air dried overnight andmeasured for latent heat content. The fabrics were then washed 5 timesper AATCC 143.

#1 #2 #3 Ingredients Weight (grams) Polymeric PCM Ex. 2 5.13 5.25 Cymel385 (Cytec Industries, Inc., 1.04 West Patterson, NJ) Bayhydur VPLS 2306(Bayer 1.18 Polymers, Pittsburgh PA) Acetone 10.68 11.79 Polymeric PCMEx. 4 30.0 Wash Durability and Latent Heat Content (J/g) Treated Fabric8.1 14.5 37.3 5x Washes 5.8 12.0 31.2

Example 6

Various polymeric PCMs were made similar to example 4 above, but themol. wt. was varied by changing the amount of peroxide initiator orchanging the polymerization solution solids.

Example 6 Polymeric PCM Molecular Weight Results

Sample DSC J/g Melt Peak Mn Mw Mz Pd 4-123, mfg at 70% solids Good 83.831.1 2670 8040 14600 3.01 4-135, mfg at 75% solids Acceptable 73.5 33.54170 21400 50400 5.13 4-144, mfg at 100% solids Poor 63.6 26.2 468039200 232400 8.38

Example 7

Above polymeric PCM, 4-123, was dried to 100% solids then added tovarious polymer fiber solutions both in the lab and in production pilotplant. These solutions were either spun into fiber or cast into films,coagulated, and dried to yield polymeric PCM modified products. SolutionA consisted of Acordis Itaconic acid func. CFP polyacrylonitrile polymerdissolved in 1:1 NaSCN:H₂O to give a 10% final solution. Solution Bconsisted of Novaceta® diacetate dissolved in water:acetone mixture togive a 26.6% solids solution in a wt. ratio of cellulosediacetate/H₂O/Acetone, 26.6/3.9/69.5. Solution C was based on Novacetapilot run using polymeric PCM produced at Ortec Inc.

Example 7 Fiber and Films

Thermocycle % Theory and Sample FP-PCM J/g Measured J/g C₆ Extr. % <Theory Sol. A 15.0 12.6 8.0 Sol. B 10.0 8.4 4.6 5.9 30 Sol. C 10.0 7.12.4 2.9 59

Those skilled in the art can readily recognize that numerous variationsand substitutions may be made in the invention, its use and itsconfiguration to achieve substantially the same results as achieved bythe embodiments described herein. Accordingly, there is no intention tolimit the invention to the disclosed exemplary forms. Many variations,modifications and alternative constructions fall within the scope andspirit of the disclosed invention as expressed in the claims.

1. An article comprising: a substrate; and a functional polymeric phasechange material bound to the substrate.
 2. An article according to claim1, wherein the functional polymeric phase change material is chemicallybound to the substrate.
 3. An article according to claim 2, wherein thechemical bonding is at least one of covalent bonding or electrovalentbonding.
 4. An article according to claim 2, wherein the bonding isaccomplished through direct bonding.
 5. An article according to claim 2,wherein the bonding is accomplished by a connecting compound.
 6. Anarticle according to claim 1, further comprising at least one ingredientselected from a group consisting of an additional functional polymericphase change material, an additional phase change material, encapsulatedphase change materials, a binder, a formulation, an additive,crosslinkers, blending polymers, compatibilizers, wetting agents, andcombinations of the foregoing.
 7. An article according to claim 1,wherein the substrate is selected from the group consisting of textiles,natural fibers, fur, synthetic fibers, regenerated fibers, woven fabric,knit fabric, nonwoven fabric, foams, paper, leather, plastic, polymericlayers, plastic films, plastic sheets, laminates or combinations of theforegoing.
 8. An article according to claim 1, wherein the functionalpolymeric phase change material comprises a reactive function selectedfrom the group consisting of an acid anhydride group, an alkenyl group,an alkynyl group, an alkyl group, an aldehyde group, an amide group, anamino group and their salts, a N-substituted amino group, an aziridine,an aryl group, a carbonyl group, a carboxy group and their salts, anepoxy group, an ester group, an ether group, a glycidyl group, a halogroup, a hydride group, a hydroxy group, an isocyanate group, a thiolgroup, a disulfide group, a silyl or silane group, an urea group, and anurethane group, and wherein the substrate comprises at least one ofcellulose, wool, fur, leather, polyester and nylon.
 9. An articleaccording to claim 2, wherein the functional polymeric phase changematerial comprises an anhydride function and the substrate comprises atleast one of cellulose, wool, fur, leather, polyester and nylon.
 10. Anarticle according to claim 2, wherein the functional polymeric phasechange material comprises an isocyanate function and the substratecomprises at least one of cellulose, wool, fur, leather, polyester andnylon.
 11. An article according to 2, wherein the functional polymericphase change material comprises a reactive function selected from agroup consisting of an amine function and an amide function and thesubstrate comprises at least one of cellulose, wool, fur, leather,polyester and nylon.
 12. An article according to claim 2, wherein thefunctional polymeric phase change material comprises a silane functionand the substrate comprises at least one of cellulose, wool, fur,leather, polyester and nylon.
 13. An article according to claim 2,wherein the functional polymeric phase change material comprises adouble bond.
 14. An article according to claim 1, characterized inhaving at least one phase change temperature in the range between −10°C. and 100° C.
 15. An article according to claim 1, characterized inhaving phase change enthalpy of at least 2.0 Joules per gram.
 16. Anarticle according to claim 1, wherein the functional polymeric phasechange material comprises a hydrophilic crystallizable section.
 17. Anarticle according to claim 1, wherein the functional polymeric phasechange material comprises a hydrophobic crystallizable section.
 18. Anarticle according to claim 1 wherein the substrate comprises at leastone of starch and modified starch.
 19. The article of claim 18 whereinthe modified starch is selected from the group consisting ofhydroxyethyl starch, hydroxypropyl starch, starch acetate, starchphosphate, starch, cationic starches, anionic starches and combinationsof the foregoing.
 20. A method of producing an article, comprisingproviding a functional polymeric phase change material, providing asubstrate; and combining the functional polymeric phase change materialwith the substrate.
 21. A method according to claim 20, wherein thesubstrate carries at least one reactive function and wherein combiningthe functional polymeric phase change material with the substratecomprises chemically reacting a functional group of the functionalpolymeric phase change material with a functional group of thesubstrate.
 22. A precursor for the production of an article, wherein theprecursor comprises a functional polymeric phase change material and atleast one other ingredient.
 23. A precursor according to claim 22,wherein the at least one other ingredient is selected from the groupconsisting of an organic solvent, an aqueous solvent, another functionalpolymeric phase change material, another phase change material,microcapsules comprising phase change material, binders, crosslinkers,blending polymers, compatibilizers, wetting agents, additives, andcombinations of the foregoing.
 24. A method of producing an articlecomprising: providing a precursor comprising a functional polymericphase change material, providing a substrate, and combining thefunctional polymeric phase change material of the precursor with thesubstrate.
 25. A method according to claim 24, wherein the substratecarries at least one reactive function and combining the functionalpolymeric phase change material of the precursor with the substratecomprises chemically reacting a functional group of the functionalpolymeric phase change material with a functional group of thesubstrate.